Manufacture of tertiary-octyl-2-benzothiazolesulfenamide



nited States Patent Ofiice 2,807,621 Patented Sept. 24, 1957 MANUFACTURE OF TERTIARY-OCTYL-Z-BENZO- THIAZOLESULFENAMIDE Robert H. Cooper, Nitro, and John J. DAmico, Charleston, W. Va., assignors to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application December 23, 1955, Serial No. 554,927

1 Claim. (Cl. 260-306.6)

The present invention relates to the manufacture of sulfenamides and particularly to benzothiazolesulfenamides in highly satisfactory yield and of excellent purity, especially as regards freedom from ordinarily occurring disulfide side reaction products. The improvements in the present invention, as hereinafter set forth in more detail, apply more specifically to tertiary-octylamine, the benzothiazolesulfenamide of which, heretofore, has not been obtainable in a state of satisfactory purity and storage stability by methods previously described.

The commercial importance of the benzothiazolesulfenamides as accelerators of the rubber vulcanization process is well known. For most satisfactory results from such use however, the aforesaid accelerators must be of as high purity as is commercially feasible, and, of most importance, must be of sufficient stability as not to undergo deleterious breakdown in normal storage time to produce unwanted products. It has been noted that such breakdown appears to be a concomitant property with the initial disulfide content of the sulfenamide. The higher the initial disulfide content, the more rapid is the increase with time of the amount of disulfide present, with a resulting change in the physical and chemical properties of the resulting mixture of products. When the disulfide content increases from an initial low quantity to from about 8 to 15% by weight, the appearance has not in many cases materially altered, but the mixture is greasy to the feel, does not pour freely as does a dry crystal, is lowered in melting point and diifers in accelerating activity from the freshly produced product of normally low disulfide content. Obviously it is much more desirable to obtain the sulfenamides initially in as pure a state as possible.

The conditions requisite for the production of a sulfenamide by the preferred new process are apparent from the following example. In a jacketed reaction vessel of suitable size and of acid resisting composition, and equipped with temperature recording means, mechanical agitation and connected with an auxiliary metal tank for containing oxidizing solution, there are added 600 parts (0.5 mole) of sodium mercaptobenzothiazole solution (13.9% concentration mercaptobenzothiazole). Additionally, for recording the pH of the reacting mixture, in order to control the course of and the end of the reaction, the reactor has installed an antimony-calomel electrode in connecgion with a suitable potentiometer. To the benzothiazole solution there were added 96.8 parts (0.75 mole) of tertiary-octylamine. The quantity of amine preferred is approximately 50% in excess of that required for the reaction but is necessary to avoid formation of undesired products. Substantially all the excess amine is, of course, recoverable at the end of the reaction period. This amine preferably is added to the thiazole at a slow rate over a period of time while agitating the mixture. At this stage of the process the pH of the mixture was 12.5 and the millivolt reading 710. After the amine was all added, agitation was continued for from 15 to 30 minutes whereupon 117.8 parts (0.30

mole) of 25% sulfuric acid were added over a period of 15-30 minutes. After all the acid had been added, the pH reading was 9.6. The mixture was then heated to and maintained between 4550 C. and, after agitating for approximately 30 minutes, there were added 292 parts (0.6 mole) of a 15.25% by Weight solution of sodium hypochlorite. The hypochlorite, which is approximately 20% theory excess, was added over about a two hour period, while agitating and maintaining the temperature limits set forth. A break in potential indicated an excess of hypochlorite, whereupon hypochlorite addition was discontinued and the mixture agitated at 45-50 C. for approximately an hour. During this period the reaction mixture should be positive to starch-iodide paper. If at any time a positive reaction is not obtained, additional hypochlorite should be added. A small amount (2 parts) of sodium sulphite was then added to destroy any excess hypochlorite. The mass was then cooled to about room temperature, and the solid product collected by suitable means, such as by centrifuging, washed and dried at a temperature of not over 50 C. The product, tertiary-octyl-2-benzothiazolesulfenamide, was obtained in several duplicating experiments in about 98% theory yield, melted at 98-99 C. and was free of disulfide.

The conditions imposed and set forth in some detail in the foregoing example have been found to be critical. A lower oxidizing temperature, a smaller excess of amine (15 to 40%), less than about 1.2 or more than about 1.4 molecular equivalents of mineral acid per mole of sodium mercaptobenzothiazole all result in a product of lower melting point, of appreciable to high disulfide content and a lower yield of product. Complete agitation and thorough mixture of the reactants at all stages are also essential. While the advantages of the invention can be secured by carrying out the reaction within the range of 45-65 C., these are about the operating limits and a range of 48-62 C. is preferred.

The sensitivity to amount of acid is illustrated by the following table. The data were obtained by reacting tertiary-octylamine as described in the foregoing example except that the ratio of acid varied. Since sulfuric acid is dibasic, the moles of acid were multiplied by two and divided by the moles of sodium mercaptobenzothiazole to express the acid as molecular equivalents of mineral acid per mole of sodium mercaptobenzothiazole.

Molecular equivalent of mineral acid per mole of Percent Percent sodium mercaptobenzothiazole yield disulfide It is intended to cover all changes and modifications of the example of the invention herein chosen for purposes of disclosure which do not constitute departures from the spirit and scope of the invention.

The present application is a continuation-in-part of copending application Serial No. 439,922, filed June 28, 1954, now abandoned.

What is claimed is:

The method of making tertiary-octyl-2-benzothiazole sulfenamide which comprises oxidizing at a temperature of 45-65 C. in aqueous medium by means of a hypochlorite a mixture of one molecular proportion of at least 13% aqueous solution of Z-mercaptobenzothiazole in the form of the sodium salt, an excess suflicient to provide optimum yield not more than one and one-half molecular proportions of tertiary-octylamine and 1.2-1.4 molecular equivalents of mineral acid.

(References on following page) References Cited in the file of this patent UNITED STATES PATENTS fIsphunkur et a1. June 30, 1936 Ashworth Dec. 30, 1941 5 Carr Feb. 3, 1942 Cooper Jan. Carr Jan. Howland Aug. Smith Ian. Moore et a1. Mar 

